High charge density metallophosphate molecular sieves

ABSTRACT

A family of highly charged crystalline microporous metallophosphate molecular sieves designated PST-17 has been synthesized. These metallophosphates are represented by the empirical formula of:
 
R p+   r A m   + M x E y PO z  
 
where A is an alkali metal such as potassium, R is a quaternary ammonium cation such as ethyltrimethylammonium, M is a divalent metal such as zinc and E is a trivalent framework element such as aluminum or gallium. The PST-17 family of molecular sieves are stabilized by combinations of alkali and organoammonium cations, enabling unique metalloalumino(gallo)phosphate compositions and exhibit the BPH topology. The PST-17 family of molecular sieves has catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of International Application No. PCT/US2017/033749 filed May 22, 2017, which application claims priority from U.S. Provisional Application No. 62/341,172 filed May 25, 2016, the contents of which cited applications are hereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention relates to a family of charged metallophosphate-based molecular sieves designated PST-17. They are represented by the empirical formula of: R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where A is an alkali metal such as potassium, R is at least one quaternary organoammonium cation such as ethyltrimethylammonium, M is a divalent metal such as zinc and E is a trivalent framework element such as aluminum or gallium. The PST-17 family of materials has the BPH topology.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which are microporous and which are formed from corner sharing [AlO_(4/2)]⁻ and SiO_(4/2) tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared are used in various industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis employing suitable sources of Si, Al and structure directing agents (SDAs) such as alkali metals, alkaline earth metals, amines, or organoammonium cations. The structure directing agents reside in the pores of the zeolite and are largely responsible for the particular structure that is ultimately formed. These species balance the framework charge associated with aluminum and can also serve as space fillers. Zeolites are characterized by having pore openings of uniform dimensions, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversion reactions, which can take place on outside surfaces of the zeolite as well as on internal surfaces within the pores of the zeolite.

In 1982, Wilson et al. developed aluminophosphate molecular sieves, the so-called AlPOs, which are microporous materials that have many of the same properties of zeolites, but are silica free, composed of [AlO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedra (see U.S. Pat. No. 4,319,440). Subsequently, charge was introduced to the neutral aluminophosphate frameworks via the substitution of SiO_(4/2) tetrahedra for [PO_(4/2)]⁺ tetrahedra to produce the SAPO molecular sieves (see U.S. Pat. No. 4,440,871). Another way to introduce framework charge to neutral aluminophosphates is to substitute [M²⁺O_(4/2)]²⁻ tetrahedra for [AlO_(4/2)]⁻ tetrahedra, which yield the MeAPO molecular sieves (see U.S. Pat. No. 4,567,029). It is furthermore possible to introduce framework charge on AlPO-based molecular sieves via the introduction both of SiO_(4/2) and [M²⁺O_(4/2)]²⁻ tetrahedra to the framework, giving MeAPSO molecular sieves (see U.S. Pat. No. 4,973,785).

In the early 1990's, high charge density molecular sieves, similar to the MeAPOs but without the Al, were developed by Bedard (see U.S. Pat. No. 5,126,120) and Gier (see U.S. Pat. No. 5,152,972). These metal phosphates (sometimes arsenates, vanadates) were based on M²⁺ (M═Zn, Co), the general formula of which, in terms of the T-atoms, T²⁺-T⁵⁺, was approximately Al⁺T²⁺T⁵⁺O₄, having framework charge densities similar to Si/Al=1 zeolites and were charge balanced by alkali cations, A⁺, in the pores. Later attempts to prepare metallophosphates of similar compositions but with organic SDAs led to porous, but interrupted structures, i.e., the structures contained terminal P—O—H and Zn—N bonds (see J. MATER. CHEM., 1992, 2(11), 1127-1134). Attempts at Al substitution in a zincophosphate network was carried out in the presence of both alkali and organoammonium agents, specifically the most highly charged organoammonium species, tetramethylammonium, but because of the high framework charge density, only the alkali made it into the pores to balance framework charge (see U.S. Pat. No. 5,302,362). Similarly, in a high charge density zincophosphate system that yielded the zinc phosphate analog of zeolite X, the synthesis in the presence of Na⁺ and TMA⁺ yielded a product that contained considerably less TMA⁺ than Na⁺ (see CHEM. MATER., 1991, 3, 27-29).

To bridge the rather large charge density gap between the MeAPOs of U.S. Pat. No. 4,567,029 and the aforementioned alkali-stabilized Me²⁺-phosphates of Bedard and Gier, Stucky's group developed a synthesis route using amines, often diamines in ethylene glycol-based reaction mixtures. They were able to make high charge density, small pore MeAPOs in which the concentrations of Co²⁺ and Al³⁺ in R(Co_(x)Al_(1-x))PO₄ were varied such that 0.33≤x≤0.9 in the so-called ACP series of materials, the aluminum cobalt phosphates (see NATURE, 1997, 388, 735). Continuing with this synthesis methodology utilizing ethylene glycol solvent and matching the amines to framework charge densities for R(M²⁺ _(x)Al_(1-x))PO₄, such that 0.4≤x≤0.5, (M²⁺+Mg²⁺, Mn²⁺, Zn²⁺, Co²⁺) the large pore materials UCSB-6, -8 and -10 were isolated (see SCIENCE, 1997, 278, 2080). Crystal dimensions isolated from that work were often on the order of hundreds of microns. Similarly, this approach also yielded MeAPO analogs of zeolite rho of the composition where RM²⁺ _(0.5)Al_(0.5)PO₄, where R=N, N′-diisopropyl-1,3-propanediamine, M²⁺=Mg²⁺, Co²⁺ and Mn²⁺. The reliance of this synthesis approach on an ethylene glycol solvent does not lend itself well to industrial scale, from both a safety and environmental point of view. While several others embraced Stucky's approach, there has been little activity in this intermediate charge density region, where 0.2≤x≤0.9 for the [M²⁺ _(x)Al_(1-x)PO_(4]) ^(x−) compositions.

Pursuing aqueous chemistry, Wright et al. used highly charged triquaternary ammonium SDAs to make new MeAPO materials (see CHEM. MATER., 1999, 11, 2456-2462). One of these materials, STA-5 with the BPH topology, (Mg_(2.1)Al_(11.9)P₁₄O₂₈), exhibited significant substitution of Mg²⁺ for Al³⁺, up to about 15%, but less substitution than seen in Stucky's non-aqueous ethylene glycol approach.

More recently, Lewis et al. developed aqueous solution chemistry using quaternary ammonium cations leading to high charge density SAPO, MeAPO, and MeAPSO materials, enabling greater substitution of SiO_(4/2) and [M²⁺O_(4/2)]²⁻ into the framework for [PO_(4/2)]⁺ and [AlO_(4/2)]⁻, respectively, using the ethyltrimethylammonium (ETMA⁺) and diethyldimethylammonium (DEDMA⁺) SDAs. These materials include ZnAPO-57 (U.S. Pat. No. 8,871,178), ZnAPO-59 (U.S. Pat. No. 8,871,177), ZnAPO-67 (U.S. Pat. No. 8,697,927) and MeAPSO-64 (U.S. Pat. No. 8,696,886). The relationship between the increasing product charge densities and reaction parameters, namely the ETMAOH(DEDMAOH)/H₃PO₄ ratios, were outlined in the literature (see MICROPOROUS AND MESOPOROUS MATERIALS, 189, 2014, 49-63). For the MeAPO compositions, the incorporation of M²⁺ observed in these systems was such that for the formulation [M²⁺ _(x)Al_(1-x)PO₄]^(x−), x˜0.3.

Applicants have now synthesized a new family of highly charged metallophosphate framework materials, designated PST-17, with higher charge densities than the MeAPOs of U.S. Pat. No. 4,567,029 and the ZnAPO materials isolated by Lewis. These metallophosphates are prepared from aqueous solution utilizing a combination quaternary ammonium and alkali cations. The PST-17 materials have the BPH topology (see DATABASE OF ZEOLITE STRUCTURES, www.iza-structure.org/databases) and have much higher metal content than the magnesioaluminophosphate STA-5 (Mg_(2.1)A_(111.9)P₁₄O₂₈), the above mentioned MeAPO that has the BPH topology (see CHEM. MATER., 1999, 11, 2456-2462.) The utility of alkali in MeAPO-based systems is uncommon and in combination with quaternary ammonium cations under the right conditions enables this system to achieve the charge densities and desired midrange compositions between the low charge density MeAPO and high charge density M²⁺-phosphate extremes.

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new family of metallophosphate molecular sieves designated PST-17. Accordingly, one embodiment of the invention is a microporous crystalline material having a three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and an empirical composition in the as synthesized form and on an anhydrous basis expressed by an empirical formula of: R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternary ammonium cation selected from the group consisting of ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium (TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.1 to about 1.0, “p” is the weighted average valence of R and varies from 1 to 2, A is an alkali metal such as Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, M is a divalent element selected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 to about 0.9, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is the mole ratio of 0 to P and has a value determined by the equation: z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851  2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w 43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

Another embodiment of the invention is a process for preparing the crystalline metallophosphate molecular sieve described above. The process comprises forming a reaction mixture containing reactive sources of R, A, M, E and P and heating the reaction mixture at a temperature of about 60° C. to about 200° C. for a time sufficient to form the molecular sieve, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of: aR_(2/p)O:bA₂O:cMO:E₂O₃ :dP₂O₅ :eH₂O where “a” has a value of about 2.1 to about 100, “b” has a value of about 0.1 to about 8.0, “c” has a value of about 0.25 to about 8, “d” has a value of about 1.69 to about 25, and “e” has a value from 30 to 5000.

Yet another embodiment of the invention is a hydrocarbon conversion process using the above-described molecular sieve as a catalyst. The process comprises contacting at least one hydrocarbon with the molecular sieve at conversion conditions to generate at least one converted hydrocarbon.

Still another embodiment of the invention is a separation process using the crystalline PST-17 material. The process may involve separating mixtures of molecular species or removing contaminants by contacting a fluid with the PST-17 molecular sieve. Separation of molecular species can be based either on the molecular size (kinetic diameter) or on the degree of polarity of the molecular species. Removing contaminants may be by ion exchange with the molecular sieve.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared a family of high charge density crystalline microporous metallophosphate compositions with the BPH topology, designated PST-17. Compared to other early MeAPO materials, the PST-17 family of materials contains much more M²⁺ and exhibits high framework (FW) charge densities that unlike the other MeAPOs, use of alkali cations in addition to organoammonium ions is necessary to balance the FW charge. The instant microporous crystalline material (PST-17) has an empirical composition in the as-synthesized form and on an anhydrous basis expressed by the empirical formula: R^(p+) _(r)A⁺ _(m)M^(3°) _(x)E_(y)PO_(z) where A is at least one alkali cation and is selected from the group of alkali metals. Specific examples of the A cations include but are not limited to lithium, sodium, potassium, rubidium, cesium and mixtures thereof. R is at least one quaternary ammonium cation, examples of which include but are not limited to ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium (TMA⁺), tetraethylammonium (TEA), tetrapropylammonium (TPA⁺) and mixtures thereof, and “r” is the mole ratio of R to P and varies from about 0.1 to about 1.0, while “p” is the weighted average valence of R and varies from about 1 to 2. M and E are tetrahedrally coordinated and in the framework, M is a divalent element selected from the group of Zn, Mg, Co, Mn and mixtures thereof, while E is a trivalent element selected from aluminum and gallium and mixtures thereof. The value of “m” is the mole ratio of A to P and varies from 0.1 to about 1.0, “x” is mole ratio of M to P and varies from 0.2 to about 0.9, while the ratio of E to P is represented by “y” which varies from about 0.10 to about 0.8. Lastly, “z” is the mole ratio of O to P and is given by the equation: z=(m+p⋅r+2⋅x+3⋅y+5)/2.

When only one type of R organoammonium cation is present, then the weighted average valence is just the valence of that cation, e.g., +1 or +2. When more than one R cation is present, the total amount of R is given by the equation: R_(r) ^(p+)=R_(r1) ^((p1)+)+R_(r2) ^((p2)+)+R_(r2) ^((p3)+)+ . . . the weighted average valence “p” is given by:

$p = \frac{{r\;{1 \cdot p}\; 1} + {r\;{2 \cdot p}\; 2} + {r\;{3 \cdot p}\; 3} + \ldots}{{r\; 1} + {r\; 2} + {r\; 3} + \ldots}$

It has also been noted that in the PST-17 materials of this invention that a portion of

M²⁺ may also reside in the pores, likely in a charge balancing role.

The microporous crystalline metallophosphate PST-17 is prepared by a hydrothermal crystallization of a reaction mixture prepared by combining reactive sources of R, A, E, phosphorous and M. A preferred form of the PST-17 materials is when E is Al. The sources of aluminum include but are not limited to aluminum alkoxides, precipitated aluminas, aluminum metal, aluminum hydroxide, aluminum salts, alkali aluminates and alumina sols. Specific examples of aluminum alkoxides include, but are not limited to aluminum ortho sec-butoxide and aluminum ortho isopropoxide. Sources of phosphorus include, but are not limited to, orthophosphoric acid, phosphorus pentoxide, and ammonium dihydrogen phosphate. Sources of M include but are not limited to zinc acetate, zinc chloride, cobalt acetate, cobalt chloride, magnesium acetate, magnesium nitrate, manganese sulfate, manganese acetate and manganese nitrate. Sources of the other E elements include but are not limited to precipitated gallium hydroxide, gallium chloride, gallium sulfate or gallium nitrate. Sources of the A metals include the halide salts, nitrate salts, hydroxide salts, acetate salts, and sulfate salts of the respective alkali metals. R is at least one quaternary ammonium cation selected from the group consisting of ETMA⁺, DEDMA⁺, HM²⁺, choline, trimethylpropylammonium, trimethylisopropylammonium, trimethylbutylammonium, tetramethylammonium (TMA⁺), tetraethylammonium (TEA), tetrapropylammonium (TPA⁺) and mixtures thereof, and the sources include the hydroxide, chloride, bromide, iodide and fluoride compounds. Specific examples include without limitation ethyltrimethylammonium hydroxide, ethyltrimethylammonium chloride, diethyldimethylammonium bromide, diethyldimethylammonium hydroxide, hexamethonium dihydroxide, hexamethonium dichloride, choline hydroxide, choline chloride, trimethylisopropylammonium hydroxide, propyltrimethylammonium chloride and tetramethylammonium chloride. In one embodiment R is ETMA⁺. In another embodiment, R is diethyldimethylammonium. In yet another embodiment, R is trimethylisopropylammonium. Finally, R may also be a combination of ETMA⁺ and at least one organoammonium cation selected from the group consisting of choline, DEDMA⁺, TMA⁺, HM²⁺, trimethylpropylammonium, trimethylisopropylammonium, trimethylbutylammonium, TEA⁺, and TPA⁺.

The reaction mixture containing reactive sources of the desired components can be described in terms of molar ratios of the oxides by the formula: aR_(2/p)O:bA₂O:cMO:E₂O₃ :dP₂O₅ :eH₂O where “a” varies from about 2.1 to about 100, “b” varies from about 0.1 to about 8, “c” varies from about 0.25 to about 8, “d” varies from about 1.69 to about 25, and “e” varies from 30 to 5000. If alkoxides are used, it is preferred to include a distillation or evaporative step to remove the alcohol hydrolysis products. The reaction mixture is now reacted at a temperature of about 60° C. to about 200° C. and preferably from about 125° C. to about 175° C. for a period of about 1 day to about 3 weeks and preferably for a time of about 1 day to about 7 days in a sealed reaction vessel at autogenous pressure. After crystallization is complete, the solid product is isolated from the heterogeneous mixture by means such as filtration or centrifugation, and then washed with deionized water and dried in air at ambient temperature up to about 100° C. PST-17 seeds can optionally be added to the reaction mixture in order to accelerate or otherwise enhance the formation of the desired microporous composition.

The PST-17 metallophosphate-based material, which is obtained from the above-described process, is characterized by the x-ray diffraction pattern, having at least the d-spacings and relative intensities set forth in Table A below.

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.3  6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m 21.50-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851  2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w 43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

The PST-17 may be modified in many ways to tailor it for use in a particular application. Modifications include calcination, ammonia calcinations, ion-exchange, steaming, various acid extractions, ammonium hexafluorosilicate treatment, or any combination thereof, as outlined for the case of UZM-4 in U.S. Pat. No. 6,776,975 which is incorporated by reference in its entirety. In addition, properties that may be modified include porosity, adsorption, framework composition, acidity, thermal stability, ion-exchange capacity, etc.

As synthesized, the PST-17 material will contain some of the exchangeable or charge balancing cations in its pores. These exchangeable cations can be exchanged for other cations, or in the case of organic cations, they can be removed by heating under controlled conditions. Because PST-17 is a large pore material, the BPH structure has 12-ring pores along the c-axis, many organic cations may be removed directly by ion-exchange, heating may not be necessary. A preferred method of removing organic cations from the pores is ammonia calcination. Calcination in air converts the organic cations in the pores to protons, which can lead to the loss of some metal, for example Al, from the framework upon exposure to ambient atmospheric water vapor. When the calcination is carried out in an ammonia atmosphere, the organic cation in the pore is replaced by NH4⁺ cation and the framework remains intact (see STUDIES IN SURFACE SCIENCE, (2004) vol. 154, p. 1324-1331). Typical conditions for ammonia calcinations include the use of gaseous anhydrous ammonia flowing at a rate of 1.1 Umin while ramping the sample temperature at 5° C./min to 500° C. and holding at that temperature for a time ranging from 5 minutes to an hour. The resulting ammonium/alkali form of PST-17 has essentially the diffraction pattern of Table A. Once in this form, the ammonia calcined material may be ion-exchanged with H⁺, NH4⁺, alkali metals, alkaline earth metals, transition metals, rare earth metals, or any mixture thereof, to achieve a wide variety of compositions with the PST-17 framework in superior condition.

When PST-17 or its modified forms are calcined in air, there can be a loss of metal from the framework, such as Al, which can alter the x-ray diffraction pattern from that observed for the as-synthesized PST-17 (see STUDIES IN SURFACE SCIENCE, (2004) vol. 154, p.1324-1331). Typical conditions for the calcination of the PST-17 sample include ramping the temperature from room temperature to a calcination temperature of 400° to 600° C., preferably a calcination temperature of 450° to 550° C. at a ramp rate of 1 to 5° C./min, preferably a ramp rate of 2 to 4° C./min, the temperature ramp conducted in an atmosphere consisting either of flowing nitrogen or flowing clean dry air, preferably an atmosphere of flowing nitrogen. Once at the desired calcination temperature, if the calcination atmosphere employed during the temperature ramp is flowing clean dry air, it may remain flowing clean dry air. If the calcination atmosphere during the ramp was flowing nitrogen, it may remain flowing nitrogen at the calcination temperature or it may be immediately converted to clean dry air; preferably at the calcination temperature the calcination atmosphere will remain flowing nitrogen for a period of 1-10 hours and preferably for a period of 2-4 hours before converting the calcination atmosphere to flowing clean dry air. The final step of the calcination is a dwell at the calcination temperature in clean dry air. Whether the calcination atmosphere during the initial temperature ramp was flowing nitrogen or flowing clean dry air, once at the calcination temperature and once the calcination atmosphere is clean dry air, the PST-17 sample will spend a period of 1-24 hours and preferably a period of 2-6 hours under these conditions to complete the calcination process.

The crystalline PST-17 materials of this invention can be used for separating mixtures of molecular species, removing contaminants through ion exchange and catalyzing various hydrocarbon conversion processes. Separation of molecular species can be based either on the molecular size (kinetic diameter) or on the degree of polarity of the molecular species.

The PST-17 compositions of this invention can also be used as a catalyst or catalyst support in various hydrocarbon conversion processes. Hydrocarbon conversion processes are well known in the art and include cracking, hydrocracking, alkylation of both aromatics and isoparaffin, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanol to olefins, methanation and syngas shift process. Specific reaction conditions and the types of feeds which can be used in these processes are set forth in U.S. Pat. Nos. 4,310,440, 4,440,871 and U.S. Pat. No. 5,126,308, which are incorporated by reference. Preferred hydrocarbon conversion processes are those in which hydrogen is a component such as hydrotreating or hydrofining, hydrogenation, hydrocracking, hydrodenitrogenation, hydrodesulfurization, etc.

Hydrocracking conditions typically include a temperature in the range of 400° to 1200° F. (204-649° C.), preferably between 600° and 950° F. (316-510° C.). Reaction pressures are in the range of atmospheric to about 3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig (1379 to 20,685 kPa g). Contact times usually correspond to liquid hourly space velocities (LHSV) in the range of about 0.1 hr⁻¹ to 15 hr⁻¹, preferably between about 0.2 and 3 hr⁻¹. Hydrogen circulation rates are in the range of 1,000 to 50,000 standard cubic feet (scf) per barrel of charge (178-8,888 std. m³/m³), preferably between 2,000 and 30,000 scf per barrel of charge (355-5,333 std. m³/m³). Suitable hydrotreating conditions are generally within the broad ranges of hydrocracking conditions set out above.

The reaction zone effluent is normally removed from the catalyst bed, subjected to partial condensation and vapor-liquid separation and then fractionated to recover the various components thereof. The hydrogen, and if desired some or all of the unconverted heavier materials, are recycled to the reactor. Alternatively, a two-stage flow may be employed with the unconverted material being passed into a second reactor. Catalysts of the subject invention may be used in just one stage of such a process or may be used in both reactor stages.

Catalytic cracking processes are preferably carried out with the PST-17 composition using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc. with gasoline being the principal desired product. Temperature conditions of 850° to 1100° F. (455° C. to 593° C.), LHSV values of 0.5 hr⁻¹ to 10 hr⁻¹ and pressure conditions of from about 0 to 50 psig (0-345 kPa) are suitable.

Alkylation of aromatics usually involves reacting an aromatic (C₂ to C₁₂), especially benzene, with a monoolefin to produce a linear alkyl substituted aromatic. The process is carried out at an aromatic: olefin (e.g., benzene:olefin) ratio of between 5:1 and 30:1, a LHSV of about 0.3 to about 6 hr⁻¹, a temperature of about 100° to about 250° C. and pressures of about 200 to about 1000 psig (1,379 to 6,895 kPa). Further details on apparatus may be found in U.S. Pat. No. 4,870,222 which is incorporated by reference.

Alkylation of isoparaffins with olefins to produce alkylates suitable as motor fuel components is carried out at temperatures of −30° to 40° C., pressures from about atmospheric to about 6,894 kPa (1,000 psig) and a weight hourly space velocity (WHSV) of 0.1 hr⁻¹ to about 120 hr⁻¹. Details on paraffin alkylation may be found in U.S. Pat. Nos. 5,157,196 and 5,157,197, which are incorporated by reference.

The conversion of methanol to olefins is effected by contacting the methanol with the PST-17 catalyst at conversion conditions, thereby forming the desired olefins. The methanol can be in the liquid or vapor phase with the vapor phase being preferred. Contacting the methanol with the PST-17 catalyst can be done in a continuous mode or a batch mode with a continuous mode being preferred. The amount of time that the methanol is in contact with the PST-17 catalyst must be sufficient to convert the methanol to the desired light olefin products. When the process is carried out in a batch process, the contact time varies from about 0.001 hour to about 1 hour and preferably from about 0.01 hour to about 1.0 hour. The longer contact times are used at lower temperatures while shorter times are used at higher temperatures. Further, when the process is carried out in a continuous mode, the Weight Hourly Space Velocity (WHSV) based on methanol can vary from about 1 hr⁻¹ to about 1000 hr⁻¹ and preferably from about 1 hr⁻¹ to about 100 hr⁻¹.

Generally, the process must be carried out at elevated temperatures in order to form light olefins at a fast enough rate. Thus, the process should be carried out at a temperature of about 300° C. to about 600° C., preferably from about 400° C. to about 550° C. and most preferably from about 450° C. to about 525° C. The process may be carried out over a wide range of pressure including autogenous pressure. Thus, the pressure can vary from about 0 kPa (0 psig) to about 1724 kPa (250 psig) and preferably from about 34 kPa (5 psig) to about 345 kPa (50 psig).

Optionally, the methanol feedstock may be diluted with an inert diluent in order to more efficiently convert the methanol to olefins. Examples of the diluents which may be used are helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e.g., methane, aromatic hydrocarbons, e.g., benzene, toluene and mixtures thereof. The amount of diluent used can vary considerably and is usually from about 5 to about 90 mole percent of the feedstock and preferably from about 25 to about 75 mole percent.

The actual configuration of the reaction zone may be any well known catalyst reaction apparatus known in the art. Thus, a single reaction zone or a number of zones arranged in series or parallel may be used. In such reaction zones the methanol feedstock is flowed through a bed containing the PST-17 catalyst. When multiple reaction zones are used, one or more PST-17 catalysts may be used in series to produce the desired product mixture. Instead of a fixed bed, a dynamic bed system, e.g., fluidized or moving, may be used. Such a dynamic system would facilitate any regeneration of the PST-17 catalyst that may be required. If regeneration is required, the PST-17 catalyst can be continuously introduced as a moving bed to a regeneration zone where it can be regenerated by means such as oxidation in an oxygen containing atmosphere to remove carbonaceous materials.

The following examples are presented in illustration of this invention and are not intended as undue limitations on the generally broad scope of the invention as set out in the appended claims. The products of this invention are designated with the general name PST-17, with the understanding that all of the PST-17 materials exhibit a structure with the BPH topology.

The structure of the PST-17 compositions of this invention was determined by x-ray analysis. The x-ray patterns presented in the following examples were obtained using standard x-ray powder diffraction techniques. The radiation source was a high-intensity, x-ray tube operated at 45 kV and 35 mA. The diffraction pattern from the copper K-alpha radiation was obtained by appropriate computer based techniques. Flat compressed powder samples were continuously scanned at 2° to 56° (2θ). Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as θ where θ is the Bragg angle as observed from digitized data. Intensities were determined from the integrated area of diffraction peaks after subtracting background, “I₀” being the intensity of the strongest line or peak, and “I” being the intensity of each of the other peaks.

As will be understood by those skilled in the art the determination of the parameter 2θ is subject to both human and mechanical error, which in combination can impose an uncertainty of about ±0.4° on each reported value of 2θ. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2θ values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the x-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, and w which represent very strong, strong, medium, and weak, respectively. In terms of 100×I/I₀, the above designations are defined as:

-   -   w=0-15; m=15-60: s=60-80 and vs=80-100

In certain instances the purity of a synthesized product may be assessed with reference to its x-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the x-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.

In order to more fully illustrate the invention, the following examples are set forth. It is to be understood that the examples are only by way of illustration and are not intended as an undue limitation on the broad scope of the invention as set forth in the appended claims.

Example 1

A Teflon beaker was charged with 150.00 g ethyltrimethylammonium hydroxide (ETMAOH, 20%, SACHEM, Inc.) and placed under a high speed stirring apparatus. Pre-ground aluminum isopropoxide (13.3% Al), 4.82 g, was added to the reaction mixture and dissolved with stirring. This was followed by the dropwise addition of 16.31 g H₃PO₄ (85.7%). Separately, 5.22 g Zn(OAc)₂*2H₂O was dissolved in 20.50 g de-ionized water and the resulting solution was added to the reaction mixture in a dropwise fashion. After completion of the addition, the reaction mixture was homogenized for an hour. Then, a solution was prepared by dissolving 1.17 g KOAc (99.4%) in 10.00 g de-ionized water. This was added to the reaction mixture in a dropwise fashion and the reaction mixture was homogenized for an additional 20 minutes post-addition. The reaction mixture was distributed among 7 Teflon-lined autoclaves and digested at autogenous pressures at temperatures of 95°, 125°, 150°, and 175° C., for either 40 or 167 hours or both. The solid products were isolated by centrifugation and washed with de-ionized water. All of the products were identified as PST-17 by powder x-ray diffraction, except for the product 175° C./167 hour digestion, which also contained a significant impurity. The representative diffraction lines of which are shown in Table 1 below for the sample from the 125° C./167 hour digestion. Elemental analysis of this same product showed it was composed of the elemental ratios Al/P=0.31, Zn/P=0.70, K/P=0.37, and N/P=0.21, consistent with the stoichiometry ETMA_(0.21)K_(0.37)Zn_(0.70)Al_(0.31)P.

TABLE 1 2-Θ d(Å) I/I₀ (%) 6.69 13.19 vs 7.54 11.72 m 13.10 6.76 w 13.40 6.60 w 14.701 6.02 w 15.39 5.75 w 18.76 4.73 w 20.14 4.41 m 21.14 4.20 m 23.75 3.74 w 24.08 3.69 m 26.50 3.36 w 27.20 3.28 w 27.43 3.25 w 28.26 3.16 w 28.56 3.12 w 29.66 3.01 m 30.08 2.97 m 30.52 2.93 w 31.06 2.88 w 31.26 2.86 w 33.31 2.69 w 33.82 2.65 w 34.25 2.62 w 35.08 2.56 w 35.74 2.51 w 36.48 2.46 w 38.02 2.36 w 38.85 2.32 w 39.21 2.30 w 39.72 2.27 w 40.76 2.21 w 42.98 2.10 w 43.42 2.08 w 47.37 1.92 w 48.84 1.86 w 49.54 1.84 w 50.14 1.82 w 51.10 1.79 w 53.06 1.72 w 53.38 1.72 w 53.96 1.70 w 55.60 1.65 w

Example 2

A Teflon beaker was charged with 174.00 g Diethyldimethylammonium hydroxide (DEDMAOH, 20% aqueous, SACHEM, Inc.) and placed under a high speed mixer. Pre-ground aluminum isopropoxide (13.2% Al), 4.97 g, was added to the reaction mixture and stirred until dissolved. This was followed by the dropwise addition of 16.69 g H₃PO₄ (85.7%). Separately, Zn(OAc)₂*2H₂O, 5.34 g, was dissolved in 25.00 g de-ionized water. This solution was added dropwise to the reaction mixture with vigorous stirring to homogenize. An additional solution was prepared by dissolving KOAc (99.4%), 1.19 g, in 12.88 g de-ionized water. This solution was added dropwise to the reaction mixture and stirred for an hour. The reaction mixture was distributed among 7 Teflon-lined autoclaves and digested at autogenous pressures at temperatures of 95°, 125°, 150°, and 175° C., for either 48, 136 hr, or 170 hours. The solid products were isolated by centrifugation and washed with de-ionized water. With the exception of the product of the 95° C./170 hour digestion, all of the products were found to contain PST-17 by powder x-ray diffraction. The representative diffraction lines are shown in Table 2 below for the PST-17 products from the 125° C./48 hour (Table 2a) and 175° C./136 hour (Table 2b) digestions. Elemental analysis of these same products showed they were composed of the following elemental ratios, 125° C./48 hr: Al/P=0.36, Zn/P=0.75, K/P=0.36, and N/P=0.25, consistent with the stoichiometry DEDMA_(0.25)K_(0.36)Zn_(0.75)Al_(0.36)P and 175° C./136 hr: Al/P=0.39, Zn/P=0.60, K/P=0.26, and N/P=0.31, consistent with the stoichiometry DEDMA_(0.31)K_(0.26)Zn_(0.60)Al_(0.39)P.

TABLE 2 Table 2a Table 2b 2-Θ d(Å) I/I₀ (%) 2-Θ d(Å) I/I₀ (%) 6.70 13.19 vs 6.72 13.14 s 7.54 11.72 s 7.56 11.69 vs 13.06 6.77 w 10.11 8.75 w 13.40 6.60 w 13.11 6.75 w 14.71 6.02 w 13.44 6.58 w 15.40 5.75 m 14.74 6.01 w 18.76 4.73 m 15.44 5.74 m 20.02 4.43 w 16.56 5.35 w 20.18 4.40 m 18.76 4.72 m 21.12 4.20 m 20.22 4.39 m 23.73 3.75 w 21.18 4.19 m 24.12 3.69 m 23.78 3.74 w 26.32 3.38 w 24.18 3.68 m 26.48 3.36 w 26.54 3.36 m 27.18 3.28 w 27.24 3.27 m 27.42 3.25 w 27.44 3.25 w 28.24 3.16 w 28.28 3.15 m 28.56 3.12 w 28.64 3.11 m 29.64 3.01 m 29.70 3.01 m 30.12 2.96 m 30.18 2.96 m 30.58 2.92 m 30.64 2.92 m 31.08 2.88 w 31.20 2.86 w 31.22 2.86 w 33.36 2.68 m 33.28 2.69 w 33.90 2.64 m 33.84 2.65 m 34.36 2.61 w 34.27 2.61 w 35.14 2.55 w 35.04 2.56 w 35.73 2.51 w 35.72 2.51 w 36.08 2.49 w 36.50 2.46 w 36.58 2.45 w 38.09 2.36 w 38.14 2.36 w 39.22 2.30 w 38.93 2.31 w 39.72 2.27 w 39.82 2.26 w 39.96 2.25 w 40.84 2.21 w 40.78 2.21 w 42.97 2.10 w 41.29 2.18 w 43.54 2.08 w 42.92 2.11 w 44.10 2.05 w 43.46 2.08 w 44.33 2.04 w 44.20 2.05 w 47.53 1.91 w 46.45 1.95 w 48.38 1.88 w 48.88 1.86 w 48.98 1.86 w 49.52 1.84 w 49.56 1.84 w 50.18 1.82 w 50.33 1.81 w 51.04 1.79 w 51.14 1.78 w 53.02 1.73 w 53.12 1.72 w 53.37 1.72 w 53.48 1.71 w 53.93 1.70 w 54.10 1.69 w 55.24 1.66 w 55.30 1.66 w 55.69 1.65 w

Example 3

A Teflon bottle was charged with 159.12 g ETMAOH (20%) followed by the addition of 6.31 g of Al-isopropoxide (Al(OiPr)₃, 98+%). The mixture was stirred in a sealed bottle until the Al(OiPr)₃ was fully dissolved. The mixture was transferred to a Teflon beaker equipped with an overhead high speed stirrer. Then, H₃PO₄ (85%), 20.95 g, was added slowly with vigorous mixing. Separately, 6.78 g Zn acetate dihydrate was dissolved in 30 g deionized water. The Zn solution was then slowly added to the Al/P/ETMAOH solution over a period of 30 minutes while mixing continued. Homogenization of the reaction mixture was continued for 30 minutes after completion of the Zn addition. In a separate beaker, 1.82 g KBr was dissolved in 25.03 g deionized water. This was then added slowly to the reaction mixture while continuing to mix. Again, mixing was continued for 30 minutes after this addition was completed. A clear solution reaction mixture was then distributed between 4×125 ml autoclaves and digested for 7 and 8 d at 150° C. The solid products were isolated by centrifugation and washed with de-ionized water. Powder X-ray diffraction showed all of the products to be PST-17 with the BPH topology. Representative diffraction lines for the PST-17 product are given in Table 3 below.

TABLE 3 2Θ d(Å) I/I₀ % 6.83 12.94 vs 7.69 11.49 m 10.24 8.63 w 13.24 6.68 w 13.55 6.53 w 14.87 5.95 w 15.55 5.70 w 18.92 4.69 w 20.30 4.37 w 21.32 4.16 w 23.91 3.72 w 24.27 3.66 m 26.66 3.34 w 27.38 3.25 w 27.60 3.23 w 28.46 3.13 w 28.76 3.10 w 29.84 2.99 w 30.26 2.95 m 30.77 2.90 w 31.27 2.86 w 31.43 2.84 w 33.51 2.67 w 34.02 2.63 w 35.26 2.54 w 36.68 2.45 w 38.24 2.35 w 39.85 2.26 w 40.14 2.24 w 40.97 2.20 w 43.22 2.09 w 43.62 2.07 w

Example 4 Na⁺ Ion-Exchange of PST-17

A Na⁺ ion-exchange was carried out on the product from the 7 d at 150° C. reaction in Example 3. A 1.75 g portion of the dried PST-17 was slurried in 29.2 g of a 6% NaCl solution. The slurry was covered and heated to 75° C. while mixing on a stir plate. The slurry was held at 75° C. for about 1 hour. The solid was then collected and washed with deionized water. This process was repeated two additional times. The solid was dried at 100° C. after the final exchange step. A Leco CHN analysis showed that the C level was reduced to 2.75 wt % after the exchange, where typically as-synthesized PST-17 contains 6.5 to 11% carbon. This demonstrates that significant portions of the organic cation may be removed directly by ion-exchange.

Example 5 NH4⁺ Ion-Exchange of PST-17

A Teflon bottle was charged with 891.07 g ETMAOH (20%, SACHEM, Inc.). A 35.31 g portion of aluminum isopropoxide (AIP, 98+%) was added and the mixture was stirred in the sealed bottle until the AIP was fully dissolved. The reaction mixture was transferred to a Teflon beaker and 117.32 g of H₃PO₄ (85%) was added slowly while mixing with an overhead stirrer. Separately, 37.95 g of zinc acetate dehydrate was dissolved in 168.00 g of deionized water. The zinc acetate solution was then slowly added to the reaction mixture over a period of 2 hours, while mixing with an overhead stirrer. The mixing was continued for 30 min after the addition was completed. In a separate beaker, 10.18 g KBr was dissolved in 25.03 g deionized water. This was then added slowly to the reaction mixture while continuing to mix with an overhead stirrer. The mixing was continued for 30 min after this addition was complete. A slightly hazy solution resulted. The solution was then transferred to a 2 L autoclave and digested for 7 days at 150° C. at autogenous pressure. The product was isolated by centrifugation, washed with deionized water and dried at 100° C. Powder x-ray diffraction showed the product to be PST-17 with the BPH topology. Representative diffraction lines for the PST-17 product are shown in Table 4a below. Elemental analysis showed the PST-17 to consist of the following elemental ratios: Al/P=0.32, Zn/P=0.71, K/P=0.37, and N/P=0.25, consistent with the empirical formula ETMA_(0.25)K_(0.37)Zn_(0.71)Al_(0.32)P. Specifically, the carbon content in this PST-17 was 7.56%.

A 20 g portion of the as-synthesized PST-17 material was then ammonium ion-exchanged. A 20 g portion of NH₄NO₃ was dissolved in 200 g deionized water. The dried PST-17 material was then added to this solution while mixing on a magnetic stir plate. The slurry was covered and heated to 75° C. for 1.5 hours. The solid was collected and washed by filtration. The exchange procedure was repeated two additional times. The solid was dried at 100° C. after the final exchange step. The ammonium ion-exchanged PST-17 was identified as such by powder x-ray diffraction; the representative diffraction lines shown in Table 4b. Leco CHN analysis showed that the carbon content in the ammonium ion-exchanged PST-17 is 0.21%, indicating that more than 97% of the ETMA⁺ SDA had been removed by ion-exchange.

TABLE 4 Table 4a Table 4b 2-Θ d(Å) I/I₀ % 2-Θ d(Å) I/I₀ % 6.72 13.15 vs 6.73 13.12 vs 7.58 11.65 m 7.61 11.61 s 10.13 8.72 w 10.15 8.71 w 13.14 6.73 w 13.19 6.71 w 13.45 6.58 w 13.46 6.57 m 14.76 6.00 w 14.81 5.98 w 15.44 5.73 w 15.47 5.72 w 16.60 5.34 w 18.86 4.70 w 18.82 4.71 w 20.22 4.39 w 20.20 4.39 w 21.29 4.17 m 21.21 4.18 w 23.89 3.72 w 22.84 3.89 w 24.21 3.67 m 24.16 3.68 m 26.63 3.35 w 26.58 3.35 w 27.08 3.29 w 27.27 3.27 w 27.38 3.25 w 27.51 3.24 w 27.62 3.23 w 28.35 3.15 w 28.44 3.14 w 28.63 3.12 w 28.68 3.11 w 29.74 3.00 w 29.82 2.99 m 30.15 2.96 m 30.19 2.96 m 30.63 2.92 w 30.71 2.91 w 31.34 2.85 w 31.16 2.87 w 33.41 2.68 w 31.41 2.85 w 33.90 2.64 w 33.53 2.67 w 35.16 2.55 w 33.96 2.64 w 35.84 2.50 w 34.23 2.62 w 36.53 2.46 w 34.44 2.60 w 38.12 2.36 w 35.30 2.54 w 38.93 2.31 w 36.60 2.45 w 39.34 2.29 w 38.21 2.35 w 39.78 2.26 w 39.83 2.26 w 40.85 2.21 w 40.93 2.20 w 43.07 2.10 w 43.19 2.09 w 43.48 2.08 w 43.58 2.07 w 44.25 2.05 w 46.14 1.97 w 46.02 1.97 w 49.77 1.83 w 46.57 1.95 w 51.36 1.78 w 48.97 1.86 w 53.32 1.72 w 49.62 1.84 w 55.70 1.65 w 50.21 1.82 w 50.66 1.80 w 51.18 1.78 w 51.69 1.77 w 53.15 1.72 w 53.44 1.71 w 54.04 1.70 w

Specific Embodiments

While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.

A first embodiment of the invention is a microporous crystalline metallophosphate material having a three-dimensional framework of M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternary ammonium cation selected from the group consisting of ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium (TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.1 to about 1.0, “p” is the weighted average valence of R and varies from 1 to 2, A is an alkali metal selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, M is a divalent element selected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 to about 0.9, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is the mole ratio of O to P and has a value determined by the equation z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851  2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w 43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w

An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where in the metallophosphate material A is potassium. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where in the metallophosphate material R is ethyltrimethylammonium cation, ETMA⁺. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where in the metallophosphate material R is the diethyldimethylammonium cation, DEDMA⁺. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where in the metallophosphate material R is the trimethylisopropylammonium cation. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where a crystalline modified form of the crystalline microporous metallophosphate comprises a three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and derived by modifying the crystalline microporous metallophosphate, the modifications comprising calcination, ammonia calcinations, ion-exchange, steaming, various acid extractions, ammonium hexafluorosilicate treatment, or any combination thereof.

A second embodiment of the invention is a method for preparing a microporous crystalline metallophosphate material having a three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternary ammonium cation selected from the group consisting of ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium (TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.1 to about 1.0, “p” is the weighted average valence of R and varies from 1 to 2, A is an alkali metal selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, M is a divalent element selected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 to about 0.9, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is the mole ratio of O to P and has a value determined by the equation z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851  2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w 43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w the process comprising forming a reaction mixture containing reactive sources of R, A, E, M and P, and heating the reaction mixture at a temperature of about 60° C. to about 200° C. for a time sufficient to form the metallophosphate molecular sieve, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of aR_(2/p)O bA₂O cMO E₂O₃ dP₂O₅ eH₂O where “a” has a value of about 2.1 to about 100, “b” has a value of about 0.1 to about 8.0, “c” has a value of about 0.25 to about 8, “d” has a value of about 1.69 to about 25, and “e” has a value from 30 to 5000. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the initial reaction mixture is a clear solution before digestion. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where A is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof and the source of A is selected from the group consisting of halide salts, nitrate salts, acetate salts, sulfate salts, hydroxide salts and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where M is selected from the group consisting of Zn²⁺, Mn²⁺, Co²⁺ and Mg²⁺ and mixtures thereof and where the source of M is selected from the group consisting of halide salts, nitrate salts, acetate salts, sulfate salts and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the source of E is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina, Al(OH)₃, alkali aluminate salts, aluminum metal, aluminum halide salts, aluminum sulfate salts, aluminum nitrate salts, precipitated gallium oxyhydroxide, gallium nitrate, gallium sulfate and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the reaction mixture is reacted at a temperature of about 125° C. to about 185° C. for a time of about 1 day to about 14 days. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where R is ethyltrimethylammonium, ETMA⁺. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where R is diethyldimethylammonium, DEDMA⁺. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising adding PST-17 seeds to the reaction mixture.

A third embodiment of the invention is a hydrocarbon conversion process comprising contacting a hydrocarbon stream with a catalyst at hydrocarbon conversion conditions to generate at least one converted product, wherein the catalyst is selected from the group consisting of a crystalline microporous PST-17 material, a modified crystalline microporous PST-17 material and mixtures thereof, where PST-17 is a crystalline microporous metallophosphate having a three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternary ammonium cation selected from the group consisting of ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium (TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.1 to about 1.0, “p” is the weighted average valence of R and varies from 1 to 2, A is an alkali metal such as Li^(t), Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, M is a divalent element selected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 to about 0.9, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is the mole ratio of O to P and has a value determined by the equation z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A

TABLE A 2Θ d(Å) I/I₀ % 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851  2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w 43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w and the modified crystalline microporous PST-17 consists of a three-dimensional framework of [M^(2+O) _(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units derived from PST-17 via the modification processes of calcination, ammonia calcinations, ion-exchange, steaming, various acid extractions, ammonium hexafluorosilicate treatment, or any combination thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the hydrocarbon conversion process is selected from the group consisting of cracking, hydrocracking, alkylation, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrofining, hydrodenitrogenation, hydrodesulfurization, methanol to olefins, methanation, syngas shift process, olefin dimerization, oligomerization, dewaxing, and combinations thereof.

Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated. 

The invention claimed is:
 1. A microporous crystalline metallophosphate material having a three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of: R^(p+) _(r)A⁺ _(m)M²⁺ _(x)E_(y)PO_(z) where R is at least one quaternary ammonium cation selected from the group consisting of ethyltrimethylammonium (ETMA⁺), diethyldimethylammonium (DEDMA⁺), hexamethonium (HM²⁺), choline [Me₃NCH₂CH₂OH]⁺, trimethylpropylammonium, trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium (TMA⁺), tetraethylammonium (TEA⁺), tetrapropylammonium (TPA⁺) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.1 to about 1.0, “p” is the weighted average valence of R and varies from 1 to 2, A is an alkali metal selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.0, M is a divalent element selected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 to about 0.9, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is the mole ratio of O to P and has a value determined by the equation: z=(m+p⋅r+2⋅x+3⋅y+5)/2 and is characterized in that it has the x-ray diffraction pattern having at least the cl-spacing and intensities set forth in Table A: TABLE A 2Θ d(A) I/I₀ ¾ 6.90-6.64 12.80-13.31  s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m  21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s   26.75-26.386  3.33-3.375 w-m 27.51-27.04  3.24-3.295 w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45  3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w  38.44-37.851  2.34-2.375 w  40.04-39.528  2.25-2.278 w  41.19-40.567  2.19-2.222 w 43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w.


2. The metallophosphate material of claim 1 where A is potassium.
 3. The metallophosphate material of claim 1 where E is aluminum.
 4. The metallophosphate material of claim 1 where R is ethyltrimethylammonium cation, ETMA+.
 5. The metallophosphate material of claim 1 where R is the diethyldimethylammonium cation, DEDMA+.
 6. The metallophosphate material of claim 1 where R is the trimethylisopropylammonium cation.
 7. A crystalline modified form of the crystalline microporous metallophosphate of claim 1, comprising a three-dimensional framework of [M²⁺O_(4/2)]²⁻, [EO_(4/2)]⁻ and [PO_(4/2)]⁺ tetrahedral units and derived by modifying the crystalline microporous metallophosphate of claim 1, the modifications comprising calcination, ammonia calcinations, ion-exchange, or the combination thereof. 